Process of making sulfuric anhydrid.



PATENTED JUNE 12; 1906.

R. IKNIETSOH.

PROCESS OF MAKING SULFUR'IG ANHYDRID.

APPLICATION TILED FEB. 18, 1901,

RUDOLF IK 'IETSOH, OF LUDWIGSHAFE N-ON-THE a ASSIGNOR, BY MESNEASSIGNMENTS, TO-GENERALCHEMICAL 'ooM PAN'Y, A CQRPOBATION or VNEWIYORK'.

flPnocsss os'mAkme ULF hIdA HYbRIbL;

No. seams.

Specification of Letters Patent,

I Patented-Inns 1.211896.-

Orlgliul m h m a, 1888, semi. aav an. new and m. applinafionfllodFebruary 151901. 'm"

.To all whom it may concern.-

Be it knownthat I, RUDOLF KNIETSCH, a

subject of the German Emperor, and a resis dent ofLudwigshafen-on-the-Rhine, German have invented a certain new and usefulocess of Making Sulfuric Anhydrid, of which the following is aspecification.

- In United States Letters Patentv No. 652,119 granted June 19, 1900 onan application tiled Jul 14, 1898, Serial No. 685,969, I stated as foows: The reaction between sulfur dioxid and oxygen only takes place atan elevated tem ature,'so that it is necessary to submit-t e gaseseither separatel or I heated chamber from a in admixture to apreliminary heati uch heat was applied y exposing the tu es to a low redheat maintained in a surrounding furnace, as shown in Raths GermanPatent No. 22,1 18, of 1883 or in Ellice-OlarkesEnglish Patent No. 3,166, of 1888, or in Haenisch and Schroeders United StatesPatent No.384,841, of 1888, or in 'Starks English Patent No. 12,028, of 1889.

During the reaction the heat of chemical union ecomes added to thatapplied, and thus the temperature at the zone 0 action mayrise to anenormous degree, even to a bright red heat, according to the richness insulfur dioxid of'the gas mixture or-to the strength of the current ofthe gases, or bot In my said patent I also described means I wherebyinstead of maintaining the oven or.

chamber in which the combination takes place at a low red heat I cooledthe contents of said chamber in such manner that the heat at. the zoneof maximum or ultimate reaction thereini. 0., the reaction thatdetermines the iercentage of SO,, in the final product was ept below thedecomposing-heat of S0,.

Onefeature ofmy present invention consists 5' g H 'as limiting to theform of apparatus ofan improved method of conducting such mate reactionshall be kept substantiall bee 7 i In the first place thedivision of thecatalytic material, as hereinafter described into H ;up into a number ofcempartmentsbytheim 's'ertion in any suitablesway of. a number of andupon'eachfl. ;plate a layer 'of contact material s placed".

low said decomposing temperature an the advantages hereof showthemselves in two di-':

rections.

ten all th d m In converte w e at com gas to pass equably through thethe thus producing ments and givmg said cooling action ai'better maximumre- 1 inde endently-supported sections, each ex e way across the passagefor the material prevents-thev acking of the mate-jri 1, an thereby enabes the passed through withoutundue material into sections resents tothe' coo action, for the remove of thejexcess 'of heat", a materialwhich is diffused by having inte'rx j vening spaces between saidsections wherein 6oases partially converted by one section v action I oft e material are under cool' while passing to the next section ofmaterial, the catalytic heat ininstalopportum't to remove the excessofheat du'e to the cat ytic action than where said heat is generated allat once in a continuous mass of material.

In said Patent No.

tact-chamber, a passage ad chamber for a coo 7 did ity thereof. v

In th'e'accompanymg' drawmgs; e 1; represents the 'contact-chamber;R. ;osaid 1 Patent No. 652,119 in=Verti0al sectionlwith the contact materialarranged forfcarry- 8o y present process s'aidfcontact ,vchamber beingcontiguous to -.a flue or as, r

sage Sf'through which the cooling in umitravels substantially asvdescribedgin said p'at- I igIZ is the same thing,.ex' cept ing'=th&t P;it contains another form ofupportforthe contact material! .Fig. 3 is ahorizontal-sec jtion on the-line A' B of ent.

tact material removed.

Although I do not wish to' be understood.

whereby" my present process-maybe carried fout, I willnowproceed'todescribe a desir .able form of apparatus for that p 'glerthe better to enable {a man s to practice my present process.

osein ored in, the

-' In my 'present apparatus the tubes icons tammg the said contactmaterial are divided gm'e perforated 'plates or. sieves,

the next place thefldwlsion'of the tam-1 0 652,1 19 I have shown 7pvarious forms of apparatus containing fa "con' acent .to said i erebythe ex ,cess of heat due to 't e'reaction is removed, and means for.con'trollin'gthe coolingpu 75 I 7 1g. 4'is a horizon,- ftal section onvthe line C D of Fig. 2 with the contact materialremoved. a 4

sufiicient to cover up the plate from wallf to" layers shall be relievedin whole or in part of mass in the contact-tube.

' as it' pressure from each other, while the gas shall have no othercourse than through the contact mass. 7

Referring now to the accompanying draw ings, a is an iron rod suitablysupported at the bottom of a contact-tube R and passing up its centralline. Over this rod anarrow tube 6 may be laced, reaching up therod tothe elevation o the lowerend' of the contact The first perforated platea is then passed down the contacttube over the rod a and rests upon thenarrow tube 7). 4 Upon this plate 0 sufficient platinized asbestos orsimilar contact mass is placed to cover up the lperforations andperiphery as aforesaid. ext a bead or short p1ece of narrow tube. dispassed down the contact-tube over the rod 11 until it is sup-. portedby the perforated late 0 or a ortion of the contact materi res t ereon.Next another perforated plate 0' is placed in position to rest on thebead (Z and is covered y a layer of contact material. This process iscontinued until the contact-tube 1s sufiiciently charged. The length ofthe beads regulates the distance apart of the contact mass layers, andthis can be varied at will.

In this construction each layer of; asbestos rests upon itsgolate, andthis-pressure is trans ferred to the ads and the narrow tube b, so

' that the asbestos as a whole is substantially relieved from pressureandthe asis subytic action, the catalytic action taking lace passesthrough the layers of cat ytic material and the non-catalytic actionoccur"- as it passes through the plates-or spaces by which such layersare separated. Of course other means can be adopted provided that theprinciples above stated be ob.- served. Thusthe erforated: supported bytripe D-D D! instead of by the narrow tubes or beads. strung upon: thecentral rod.

It will be observed that in gaseous mixture containing SO, and Ois-firstsubjected to catalytic action suflici'ent to effect only a partialconversioninto S0,. Then the catalytic process is discontinued, to beresumed next catalytic layer, andthus periods ofcata- -.lytic action andof comparative freedom from chemical activity succeed each other untilthe desired conversion: has-- iected' to successivecatalytic annon-cataplate's: can be my process the containing-sulfur dioxidas soonas the mixture reaches-thethe decomposing-tam better results" than thecontinuous or singlestep process previously employed, for the reasonthatfa partial conversion produces a much lowerdegree of heat and notonly prolongs thelife of the platinum contact mass, but renders theeffect of the cooling agency much. more rapid andcertain. This coolingagency operates during the'periods of interruption which intervenebetween the successiv'e catalytic instalments, and therefore at a timewhen no chemical action occurs to counteract the cooling influence, .sothat the latter is all the more energetic. Furthermore, the cooling alsotakes place during the catalytic instalments, so that the excess of heatdue to the reaction is removed both-during the catalytic process properand during the intervals betweenthe catalytic instalments.

In the articular case illustrated by the lie cooling agency is appliedexternally to the vessel in which the gases are contamed-during suchcatalytic instalments and intervening interruptions, so that the coolingagent is notmixed 1n any way with the gases undergoing. conversion.

This application is filed as a division of application, Serial No.687,912, filed August 6, 1898, in which the apparatus herein describedis claimed. Therefore the process and nop said apparatus is claimedherein.

1.- The process of manufacturing sulfuric anhydrid which consists insubjecting gas containing sulfur dioxid and oxygen to suecessivecontacts with separated bodies of contact material by which theconversion is effected in instalments while maintaining the zone ofultimate reaction substantially below the decomposing temperature of SOby. a cooling action intermediate between said contacts.

'2. The process of manufacturing anhydrid which consists. in subjectinggas containing sulfur dioxid andoxygen to successive contacts with soarated bodies of contact material bywhic theconversionis efiected ininstalments while main aining-the zone of ultimate reactionsubstantiaslgbelow the decompo temperature of by a cooling action: t'h Intermediatebetween andlduring-saidcontacts. V

3; The process of-- manufacturing sulfuric anhydrid': which consists insubjecting gasand oxygen to suecessive contacts with so arated bodies ofcontact. materialby whic v the conversion isefiected ininstalmentswhilemaintaining-the pressure at Substantiall that of the atmosphere or belowand w e maintaining the zone ofi ultimate reaction below nature of SO,-cooling; aotionintermediate between sai con-.- 4-. The process-ofsulfuric anhydrid which consists in passing a gas containin sulfurdioxid and oxygen through se arate bodies of contact material b j w ch te conversion'is-eflected in insta ments while removing from the gasesintermediate between said contacts excess of wheat due to the reaction.

ing tem -ments while maintaining the zone of ultimate reactionsubstantially below the decomposing temperature of SO, b an externalcool ing action both interme iate between and I during said contacts.

7. The process of manufacturing sulfuric anhydrid which consists in.subjecting gas containing SO, and O to successive contacts withseparated bodies of contact material b which the conversion is effectedin instaments while maintaining the pressure. at sub stantiall ,that ofthe atmosphere or below, and while maintaining the zone of ultimatereaction substantiallybelow the decomposan external cooling temperatureof SO by d etween sai coning action intermediate tacts.

' 8. The process of making sulfuric anhydrid which consists in passing agas containing SO, and 0 through separated bodies of contact material bwhich the conversion is effected in insta ments while removi n from thegases intermediate between sai contacts, excess of heat due to thereaction, by external cooling.

'9. The recess of making sulfuric anhydrid, whicli consists insubjecting a gaseous mixture containing SQ and O to catalytic actionsufficient to effect only a partial conversion into S0,, thendiscontinuing the catalytic action, and after such interruption againsubjecting the mixture to catal tic action to continue the conversioninto S 10. The process of makingsulfuric anhydrid, which consists insubjecting a gaseous mixture containing SO, and -O to catalytic actionsufiicient to effect onlya partial conversion into S0,, thendiscontinuing the catalytic action and cooling the partiallyconvertedmixture during such period of interruption, and thereupon againsubjecting the mixture to catalytic action to carry the conversionfurther.

11. The process of making sulfuric anhydrid, which consists insubjecting a gaseous mixture containing S0 and O to catalytic actionsuflicient to effect only a partial conversion into S0,, andsimultaneously employing a cooling agency to remove heat due to thecatalytic reaction, then discontinuing the catalytic action while stillcontinuing the cooling action, and after such interruption againsubjecting the mixture to cata- -'1 tie action to continue theconversion into 0 while at the same time continuing the coolin action toremove heat dueto this secon catalytic reaction.

12. The process of making sulfuric anhydrid which consists in subjectinga gaseous mixture containing SO, and O to catalytic action sufficient toeflect only a partial conversion into SO then discontinuing thecatalytic action, and during such interruption cooling the gaseousmixture by an ex-- ternally-applied agent kept separated from the saidgaseous mixture, and after such interruption subjecting the resultingmixture of partially converted and unconverted gases, in its originalamount, to catalytic action to continue the conversion into 80,.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

RUDOLF KNIETSCH.

Witnesses: v

ERNEST F. EHRHARDT. JACOB ADRIAN.

It'is hercbycertified that in Letters Patent No. 823,472, granted June12,1906, upon the application of Rudolf Kuietsch, ofLudwigshafen-on-the-Rhine, Germany, for

an improvement in "Processes of Making Sulfuric Anhydrids, an errorappears in the printed specification requiring correction, as follows:In line 64, page 2, t he word frictional should read fractional; andthat the said Letters Patent should be read with this correcticuithereinthat the same may conform to the record of the case in the PatentOffice.

Signed and sealed this 3d day ofJu1y,.A. 1);, 1906.

[swan] E. B. MOORE,

Acting Commissioner of Patents.

which consists in passing a gas containin sulfur dioxid and oxygenthrough se arate bodies of contact material b j w ch t econversion'is-eflected in insta ments while removing from the gasesintermediate between said contacts excess of wheat due to the reaction.

ing tem -ments while maintaining the zone of ultimate reactionsubstantially below the decomposing temperature of SO, b an externalcool ing action both interme iate between and I during said contacts.

7. The process of manufacturing sulfuric anhydrid which consists in.subjecting gas containing SO, and O to successive contacts withseparated bodies of contact material b which the conversion is effectedin instaments while maintaining the pressure. at sub stantiall ,that ofthe atmosphere or below, and while maintaining the zone of ultimatereaction substantiallybelow the decomposan external cooling temperatureof SO by d etween sai coning action intermediate tacts.

' 8. The process of making sulfuric anhydrid which consists in passing agas containing SO, and 0 through separated bodies of contact material bwhich the conversion is effected in insta ments while removi n from thegases intermediate between sai contacts, excess of heat due to thereaction, by external cooling.

'9. The recess of making sulfuric anhydrid, whicli consists insubjecting a gaseous mixture containing SQ and O to catalytic actionsufficient to effect only a partial conversion into S0,, thendiscontinuing the catalytic action, and after such interruption againsubjecting the mixture to catal tic action to continue the conversioninto S 10. The process of makingsulfuric anhydrid, which consists insubjecting a gaseous mixture containing SO, and -O to catalytic actionsufiicient to effect onlya partial conversion into S0,, thendiscontinuing the catalytic action and cooling the partiallyconvertedmixture during such period of interruption, and thereupon againsubjecting the mixture to catalytic action to carry the conversionfurther.

11. The process of making sulfuric anhydrid, which consists insubjecting a gaseous mixture containing S0 and O to catalytic actionsuflicient to effect only a partial conversion into S0,, andsimultaneously employing a cooling agency to remove heat due to thecatalytic reaction, then discontinuing the catalytic action while stillcontinuing the cooling action, and after such interruption againsubjecting the mixture to cata- -'1 tie action to continue theconversion into 0 while at the same time continuing the coolin action toremove heat dueto this secon catalytic reaction.

12. The process of making sulfuric anhydrid which consists in subjectinga gaseous mixture containing SO, and O to catalytic action sufficient toeflect only a partial conversion into SO then discontinuing thecatalytic action, and during such interruption cooling the gaseousmixture by an ex-- ternally-applied agent kept separated from the saidgaseous mixture, and after such interruption subjecting the resultingmixture of partially converted and unconverted gases, in its originalamount, to catalytic action to continue the conversion into 80,.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

RUDOLF KNIETSCH.

Witnesses: v

ERNEST F. EHRHARDT. JACOB ADRIAN.

It'is hercbycertified that in Letters Patent No. 823,472, granted June12,1906, upon the application of Rudolf Kuietsch, ofLudwigshafen-on-the-Rhine, Germany, for

an improvement in "Processes of Making Sulfuric Anhydrids, an errorappears in the printed specification requiring correction, as follows:In line 64, page 2, t he word frictional should read fractional; andthat the said Letters Patent should be read with this correcticuithereinthat the same may conform to the record of the case in the PatentOffice.

Signed and sealed this 3d day ofJu1y,.A. 1);, 1906.

[swan] E. B. MOORE,

Acting Commissioner of Patents.

It is hereby cvrtified that in Letters Patent No. 823,472, granted June12, 1906, upon the appIicatiou of Rudolf Knietsc-h, ofLudwigshafen-on-the-Rhine, Germany, for an improvement in "Processes ofMaking Sulfuric Anhydrids, an error appears in the printed specificationrequiring correction, as follows: In line 64, page 2, the wordfrictional should read fractional; and that the said L'dters Patentshould be read with this correction therein that the same may conform tothe record of the case in the Patent Office.

Signed and sealed this 3d day ofJuly, A. D., 1906.

[SEAL] E. B. MOORE,

Acting Commissioner of Patents.

